US3632565A - Water-insoluble aryl-azo aryl dyestuffs containing a thienyl or furyl carboxamido group - Google Patents

Water-insoluble aryl-azo aryl dyestuffs containing a thienyl or furyl carboxamido group Download PDF

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Publication number
US3632565A
US3632565A US757478A US3632565DA US3632565A US 3632565 A US3632565 A US 3632565A US 757478 A US757478 A US 757478A US 3632565D A US3632565D A US 3632565DA US 3632565 A US3632565 A US 3632565A
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amino
groups
aryl
water
parts
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US757478A
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Hans-Joerg Angliker
Richard Peter
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BASF Schweiz AG
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Ciba AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes

Definitions

  • Dyestuffs that are of special interest are those corresponding to the formula in which X, A, R R and R have the meanings given above and A represents a substituted benzene residue or a monocyclic or bicyclic heterocyclic residue.
  • Dyestuffs in which X represents a methyl or methoxy group or a hydrogen atom and R represents either a substituted furan ring or a substituted or unsubstituted thiophene ring are especially preferred.
  • the groups R and R may be alkyl groups containing 1 to 4, preferably 2 to 4 carbon atoms, for example, methyl, ethyl, n-propyl or n-butyl groups, which may be substituted in the usual manner, with groups such as C alkoxy, hydroxy, nitro, C carbalkoxy, formylamino, acetaylamino, acetoxy, diacetoxy, C alkylsulfonyl, C alkyloxycarbonyloxy, B-(p-chlorobenzenesulfonyl)- ethyl, fi-methyl-carbamyloxyethyl, fl-phenylcarbamyloxyethyl, 'y-acetamido-propyl, 8-(para-nitrophenoxy)-ethyl, f3 (parahydroxyphenoxy) ethyl, fl-(fl-acetylethoxycarbonyl)-ethyl,
  • the groups R and R preferably contain not more than 18 carbon atoms.
  • the residues R and R are preferably alkyl groups substituted by hydroxy, alkoxy, cyanoalkoxy, acyloxy or cyano groups.
  • the residue R is a heterocyclic ring such as thionyl, tetrahydrofuryl, tetrahydrothionyl and substituted furyl or thionyl, wherein the substitutent is selected from the group consisting of alkyl of up to 4 carbon atoms, chloro, carboxy, carbomethoxy, paranitrophenyl and parachlorophenyl, and which must be substituted when it contains an oxygen atom as hetero atom.
  • Suitable substituents are, for example, aryl groups, alkyl groups containing not more than 4 carbon atoms, chlorine atoms or carboxyl groups, or an alkylene chain bound on both sides to the hetero ring.
  • the diazo components preferably correspond to the formula in which Y represents a hydrogen or a halogen atom or an alkyl, alkoxy, nitro, cyano, carbalkoxy or arylsulphonyl group and Z represents a hydrogen or a halogen atom or an alkyl, alkoxy, phenoxy, cyano or trifiuoromethyl group. More particularly, Y may be hydrogen, chloro, bromo, lower alkyl, lower alkoxy, nitro, cyano, lower carbalkoxy or phenylsulphonyl, and Z may be hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy, cyano or trifiuoromethyl.
  • diazo components 1-amino-4-chlorobenzene, 1-amino-4-bromobenzene, 1-amino-4-methylbenzene, 1-amino-4nitrobenzene, 1-amino-4-cyanobenzene, l-amino-2,S-dicyanobenzene, 1-amino-4-methylsulphonylbenzene, 1-amino-4-carbomethoxybenzene, 1-amino-2,4-dichlorobenzene, 1-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, l-amino-Z-carbomethoxy-4-nitrobenzene, l-amino
  • Z-aminothiazole Z-amino-S-nitrothiazole, 2-amino-5-cyanothiazole, 2amino-4-methyl-S-nitrothiazole, 2-amino-4-methylthiazole,
  • 2-amino 4'-nitro -phenylthiazole, 2-amino-fi-chlorobenzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-nitrobenzthiazole, Z-amino-1,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole, 3-methylmercapto-5-amino1,2,4-thiadiazole, and 3-methylsulphony1-5-amino-1,2,4-thiadiazole.
  • the coupling components preferably correspond to the formula O-mcmcmooomn l NHCORs in which X represents a hydrogen atom or an alkyl or alkoxy group, such as hydrogen, methoxy, ethoxy or methyl, R represents a five-membered heterocyclic residue, for example, an aromatic residue, for example, a furan or thiophene residue or a saturated residue, for example, a tetrahydrofuran or tetrahydrothiophene residue and R represents an alkyl, lower alkyl phenyl or heterocyclic residue.
  • the residues represented by the symbol R in the coupling components may also be derived from sulpholanecarboxylic acids of the formula CH;,CH2
  • CH2 CH2 so which may carry further substituents bound to the sulpholane ring, or they may be derived from pyrrole-2- carboxylic acid.
  • the single coupling component may also be replaced by a mixture of diiferent coupling components.
  • the afiinity and building-up properties of the dyestutf mixtures so obtained are better than those of the unitary dyestufis.
  • Diazotization of the above-mentioned diazo components may be carried out by methods known per se, for example, with the aid of a mineral acid, especially hydrochloric acid, and sodium nitrite, or, for example, with a solution of nitrosyl-sulphuric acid in concentrated sulphuric acid.
  • Coupling may also be carried out by a method known per se, for example, in a neutral to acid medium, if necessary, in the presence of sodium acetate or a similar buffer which influences the rate of coupling, or a catalyst, for example, pyridine or a salt thereof.
  • the dyestuffs formed can easily be separated from the coupling mixture, for example, by filtration, because they are substantially insoluble in water.
  • the dyestufis of the present invention are eminently suitable for dyeing and printing materials, especially fibres and fabrics, made, for example, from cellulose triacetate, polyacrylonitrile and polyamides, but especially from aromatic polyesters. They produce on these materials strong dyeings possessing excellent properties of fastness, especially excellent fastness to light, sublimation and rubbing.
  • the dyeings may also be subjected to permanent press processing, for example, the Koratron process. Dyeing produced with the new dyestuffs which have been thus Lreated display excellent fastness to wet treatments and eat.
  • the new dyestuffs are advantageously used in a state of fine division, and dyeing is carried out in the presence of a dispersing agent, for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents.
  • a dispersing agent for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents.
  • a dispersing agent for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents.
  • a dispersing agent for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents.
  • Such dyestuff preparations may be obtained in a known manner, for example, by reprecipitating the dyestuff from sulphuric acid and grinding the suspension so obtained with sulphite cellulose waste liquor. If necessary,
  • a swelling agent to the dyebath, or more especially to carry out the dyeing process under superatmospheric pressure at a temperature above 100 C., for example, at 120 C.
  • Suitable swelling agents are aromatic carboxylic acids, for example, benzoic acid and salicyclic acid; phenols for example, orthoor para-hydroxydiphenyl; aromatic halogen compounds, for example, chlorobenzene, orthodichlorobenzene and trichlorobenzene; and phenylmethylcarbinol or diphenyl.
  • the new dyestuffs are also specially suitable for application by the so-called thermofixation process in which the material to be dyed is impregnated at a temperature not exceeding 60 C. with an aqueous dispersion of the dyestuif which advantageously contains 1 to 50% of urea and a thickening agent, especially sodium alginate, and then squeezed in the usual manner.
  • the impregnated material is advantageously squeezed so as to retain 50 to 100% of its dry weight of dye-liquor.
  • the material so impregnated is heated to a temperature above 100 C., for example, to a temperature within the range of from 180 to 220 C., advantageously after drying, for example, in a current of warm air.
  • thermofixation process is especially suitable for the dyeing of union fabrics made from polyester fibres and cellulosic fibres, especially cotton.
  • the padding liquor contains dyestuffs suitable for dyeing cotton, especially vat dyestufls, or reactive dyestuifs, that is to say, dyestuffs capable of being fixed on the cellulosic fibre with formation of a chemical bond, for example, dyestufis which contain a chlorotriazine or chlorodiazine residue.
  • an agent capable of binding acid for example, an alkali metal carbonate, an alkali metal phosphate, an alkali metal borate or an alkali metal perborate, or mixtures thereof.
  • an agent capable of binding acid for example, an alkali metal carbonate, an alkali metal phosphate, an alkali metal borate or an alkali metal perborate, or mixtures thereof.
  • the dyestuffs of the invention reserve well on wool, they are eminently suitable for dyeing union fabrics made from polyester fibre and wool.
  • the dyeings obtained are advantageously subjected to an after-treatment, for example, by heating with an aqueous solution of a non-ionic detergent.
  • the dyestuffs may also be applied by printing processes.
  • a printing paste is used which contains, for example, in addition to the usual printing adjuvants, for example, thickening and wetting agents, the finely divided dyestufr', if necessary, in admixture with one of the above-mentioned cotton dyestuffs, if necessary, together with urea and/or an agent capable of binding acid.
  • EXAMPLE 1 0.7 part of sodium nitrite is introduced into 15 parts of sulphuric acid and the batch is stirred. 1.63 parts of 2-cyano-4-nitroaniline are then added at a temperature of 20 to 25 C., the whole is stirred for one hour, discharged on to parts of ice and the excess of nitrite is destroyed with sulphamic acid.
  • a solution of 3.9 parts of N-bis-acetoxyethyl-3- thienoylaminoaniline in 25 parts by volume of dimethylformamide is added dropwise to the solution so obtained at a temperature not exceeding 10 C., the batch is stirred for three hours and then neutralized with 30% NaOH. The dyestuff is then isolated by filtration and dried. It dyes polyester a violet shade.
  • EXAMPLE 2 1.73 parts of 2-chloro-4-nitroaniline was mixed with 20 parts of water and 3 parts by volume of concentrated hydrochloric acid, the batch is cooled to 0 C. and then diazotization is effected with 6 parts by volume of 2 N- sodium nitrite solution. The batch is stirred for one hour, filtered, and the excess of nitrite is destroyed with sulphamic acid.
  • a solution of 3.9 parts of N-bis-acetoxyethyl-3-thienoylaminoaniline in 25 parts by volume of dimethylformamide is added dropwise to the solution so obtained at a temperature of 0 to 10 C., the batch is stirred for 3 hours and is then neutralized with 30% sodium hydroxide solution.
  • the dyestuflf of the formula is isolated by filtration and dried. It dyes polyester fibres a bluish red shade possessing excellent fastness to light and sublimation.
  • the following table lists components for further dyestuffs.
  • the dyestuffs may be obtained by coupling the diazo compounds of the anilines listed in Column I with the coupling components listed in Column II.
  • the shades obtained on polyester fibres are indicated in Column III.
  • N-bis-fl-acetoxyethyl3-aminoaniline 620 parts of N-bis-fi-acetoxyethyl-3-nitroaniline are hydrogenated in 2,000 parts of absolute alcohol in the presence of Pd/ carbon, the solvent is removed in vacuo, and the residue is distilled in a high vacuum.
  • the other coupling components may be obtained in an analogous manner.
  • Dyeing procedure 1 part of the dyestulr' obtained in the manner described in Example 1 is ground Wet With 2 parts of a 50% aqueous solution of the sodium salt of 1,1 dinaphthylmethane 2,2 disulphonic acid and the batch is dried.
  • the dyestufi preparation so obtained is mixed with 40 parts of a 10% aqueous solution of the sodium salt of N benzyl-y-heptadecylbenzimidazole disulphonic acid, and then 4 parts of a 40% acetic acid solution are added.
  • a dyebath of 4,000 parts is prepared therefrom by dilution with Water.
  • a water-insoluble azo dyestuff of the formula A-N N -N III-(3011a R in which A represents a diazo component of the benzene series, R represents hydrogen or alkyl having up to 4 carbon atoms, R and R each represents hydrogen, un-
  • a water-insoluble monoazo dyestuff as claimed in claim 1 of the formula 5.
  • a water-insoluble monoazo dyestuff as claimed in claim 1 of the formula 14 6.

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  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US757478A 1967-09-07 1968-09-04 Water-insoluble aryl-azo aryl dyestuffs containing a thienyl or furyl carboxamido group Expired - Lifetime US3632565A (en)

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Application Number Priority Date Filing Date Title
CH1252467A CH489571A (de) 1967-09-07 1967-09-07 Verfahren zur Herstellung von wasserunlöslichen Azofarbstoffen

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US757478A Expired - Lifetime US3632565A (en) 1967-09-07 1968-09-04 Water-insoluble aryl-azo aryl dyestuffs containing a thienyl or furyl carboxamido group
US00116639A Expired - Lifetime US3751405A (en) 1967-09-07 1971-02-18 Water-insoluble azo dyestuff containing a 3-(2'-thienoyl-or furoylamino)aniline group

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US00116639A Expired - Lifetime US3751405A (en) 1967-09-07 1971-02-18 Water-insoluble azo dyestuff containing a 3-(2'-thienoyl-or furoylamino)aniline group

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US (2) US3632565A (enrdf_load_stackoverflow)
BE (1) BE720489A (enrdf_load_stackoverflow)
CH (1) CH489571A (enrdf_load_stackoverflow)
FR (1) FR1581289A (enrdf_load_stackoverflow)
GB (1) GB1229265A (enrdf_load_stackoverflow)
NL (1) NL6812770A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878189A (en) * 1973-07-02 1975-04-15 Eastman Kodak Co Azo dye compounds from amino-1,2-benzisothiazolon-1,1-dioxides
US4271071A (en) * 1979-08-02 1981-06-02 Eastman Kodak Company Heterocyclic monoazo compounds from alkyl-3-(phenylamino)butyrates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2557686A1 (de) * 1975-12-20 1977-06-30 Basf Ag Farbbildner fuer kopierverfahren
US4788069A (en) * 1987-03-27 1988-11-29 The Coca-Cola Company Intensely sweet L-aspartyl-3-(bicycloalkyl)-L-alanine alkyl esters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878189A (en) * 1973-07-02 1975-04-15 Eastman Kodak Co Azo dye compounds from amino-1,2-benzisothiazolon-1,1-dioxides
US4271071A (en) * 1979-08-02 1981-06-02 Eastman Kodak Company Heterocyclic monoazo compounds from alkyl-3-(phenylamino)butyrates

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Publication number Publication date
CH489571A (de) 1970-04-30
GB1229265A (enrdf_load_stackoverflow) 1971-04-21
NL6812770A (enrdf_load_stackoverflow) 1969-03-11
BE720489A (enrdf_load_stackoverflow) 1969-03-06
US3751405A (en) 1973-08-07
FR1581289A (enrdf_load_stackoverflow) 1969-09-12

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